Ortho-oxy-monoazo dye and process of making same.



riniaren $TATE PATENT onnrcn WILHELM HERZBERG AND OSCAR SPENGLER, OF BERLIN, GERMANY, ASSIGNORS 'IO ACTIEN GESELLSCHAFT FUR ANlLIN FABRIKATION, OF BERLIN, GERMANY.

ORTHO-OXY-MIONOAZO DYE AND PROCESS OF MAKING SAIME.

Specification of Letters Patent.

Application filed June 24, 1907.

Patented Dec. 8, 1908.

Serial No. 880,621.

T 0 all whom it may concern:

Be it known that we, WILIIELM l-Innznnnc and ()scAn SPENGLER, subjects of the lmeror of Germany, residing at Berlin, llagelsergerstrasse 10", and Berlin, Lohmiihlenstrasse 67, Germany, have invented certain new and useful 1m )rovements iii-New Ortho- Oxy-Monoazo Coloringdtlatters and Processes of Making the Same, of which the following is a specification.

The present invention relates to new ortho oXyazo-coloring matters derivedv from 'picramic acid and is based on the observation that by treating an azo dyestull ol' the following general formula:

cde nznn \\\(NO2)2 wherein it represents an acid such as a naphthoisulfonic acid, an amidonaphtlrolsulfonic acid, a naphthylaminsullonic acid, a dioxyliaphthalenesulfonic acid or the like, with a hydrosultid of an alkaline earth metal there are obtained the corresponding nitroamidodyestuil's, the reaction giving a good yield. This result is very sur rising because by the action of sodium sulii the aforesaid dinitrodyestufl's cannot be converted into these ni- 'troamtile-compounds, decomposition occur ring in this case to a great extent or even completely. The dyestuffs thus roduced possess the following general iormu a:

is r in which formula It represents a suitable azodycs'tul'l' component of the naphthalene series as above set forth; they dye wool from an acid bath, generally speaking, from brown to black shades, whichshades by a subsequent treatment with oxidizing chrom'luni compounds are converted into from dark brown to black or blackish olive green tints, which tints are, generally speaking, very fast to milling and potting.

In carrying out the reaction 1t IS not nec essary to use such a hydrosullid in the isolated form; instead there may be used for instance a mixture of sodium suliid and a suitable salt ol an alkaline earth metal, which mixture is preferably prepared in solution immediately before carrying out the operation.

The following example illustrates the invention, the parts being by weight: From 17,

L part of picramic acid and 22.2 parts of the sodium salt of 2.(S-naphtholsulfonic acid there is prepared in the usual manner a monoazo-dyestufl. This dyestuil is then, in the I form of a rather thick paste, poured into 150 parts of water, and to this mixture are added 6 parts of calcium hydrate (slakcd lime), in order to fix the Oil-groin of the sodium naphtholsullonate. Alter heating the mass to 90-10() centigrade a solution of calcium hydrosullid is introduced which is prepared by dissolving 65 parts of crystallized sodium suliid and 32 parts of dry calcium chlorid together in 100 parts of water and filtering the solution thus obtained. The reaction, 71. c. the reduction ofthc nitro-group inthe amdyestufl, proceeds very quickly. The reaction being finished, the solution is feebly acidified with acetic acid and the dyestuil is then precipitated by adding common salt, whereaftcr it is obtained by filtering, pressing and drying. The product thus obtained produces on wool in an acid bath brownish tints, which by a subsequent treatment with oxidizing chromium compounds is converted into a very dark brown red. The tints thus obtained are distinguished by a very great lastncss to milling and potting.

According to the method given in the foregoing exam )lC a great number of monoazo-dycstull's derived from picramic acid may be reduced, thus forming a large series of new nitro-aniido-ortho-oxyazo-dycstu'lfs. Thus for instance from the following sulfonie acids of the naphthalene series the corresponding nitro-amido-dycstull ..ma be obtained which produces tints on woo as given in the following table.

By after-treatment with a bichromate changing to- I In acid bath-- I a 1.8 amidonaphthol- 4-sn1fonic acid. 2.5 amidonaphthol- 7sulfonic acid.

1 dark re d-brown.

dark reddish brown.

blucblack.' greenish black.

; recl-btown. brownish black.

2.8- amidonaphtholl brown. brown-black.

6-sulionic acid. 1 1.4-naphthyl aminred-brown. greenish black.

sulionic acid. 1 2.6-naphthylamini yellow-brown. greenish brown.

sulIonic acid. 7 LB-dioxynaphthnl violet. greenish black.

Iene-3.6-disulionic l acid. i

It is obvious to those skilled in the art that ourpresent invention is not limited to the foregoing example orto the details given therein. For instance, instead of the mixture of sodium sulfid and calcium chlorid used in the foregoing example a mixture of sodium sulfid or potassium suliid with a suitable salt of another alkaline earth metal, such as for instance barium chlorid, may be employed. Moreover, the respective alkali-monosu id and of the salt of the alkaline earth metal may vary to some extent; more especially these proportions as Well as the temperature at which the reaction is carried-out, and the duration of the heating'depend upon the special nature of the monoazo-dyestulf to be reduced and must be selected accordingly in order to obtain the best results.

Having now described our invention and the manner in which the same to be per: formed What we claim is,-

l. The herein-before described process for the production of new ortho-oxy-nionoazocoloring matters of t 1e general formula:

dyestuh component or ries as set forth in the fore tion, by acting with a hydrosu line earth metal upon nonoazwdveetull obtained diazotizing combining the dia" an azo-dyestuff-cc..- lene series.

2. As new "a ortho-oxy-zn:

manufacture the new ing matters of the above giver eneral 1U rule, which may obtained l acting with a hydrosulfid of an alkaline metal upon a nienoazo-dyestuii" obtl. ed by diazotizing picrarnic acid and ccmbining the diam-compound formed 1proportions of the i ace r21 with a suitable azo-dyestuff-component of the naphthalene series, which dyestuffs dye WOOl from an acid bath shades varying from brown to black, which shades on a subscqucnt treatment with an oxidizing chromium compound are converted into ,from dark brown to deep black tints, these tints being distinguished by a very great fastness to milling and potting, and which coloring 1nat ters by the action of a strong reducing agent are split up, whereby results 2.4,6-tria1nidophenol besides the amide-derivative of the naphthol-compou'nd used in iorming the parent nionoazo-dyestufi' derived from picrarnic acid.

3. As a new article of manufacture the new ortho-oXy-monoazo-dyestufl of the ion mula:

amidophenol "*esides l.2-a1nidonaphthol-osullonic acid, this dycstu'll' being in the sha oe of its sodium salt'when pulverized a dark brown powder, ha ing a metallic luster, which sodiumsalt dissolves in water to a blackish violet colored solution, WhiGh'SOldtion on addition of acetic acid aseu brownqvellow coloration and wliic on addqion of hydrochloric acid brown-yelloW preci 't addition of s brown coloration, "Hilt a the win this sonium ,ili'ui'ic acid 'to a rub which solution on ad prcc nn iarin v n icc separ and win able 2 HENRY Hiisrnra, Wotnarraa rl' .Ur'r.

h tints i agent is split up, resulting thereby are u-i- 

